CN1258690A - Preparation of composite nanometer polyimide/clay film with very low thermal expansion coefficient - Google Patents
Preparation of composite nanometer polyimide/clay film with very low thermal expansion coefficient Download PDFInfo
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- CN1258690A CN1258690A CN 00101315 CN00101315A CN1258690A CN 1258690 A CN1258690 A CN 1258690A CN 00101315 CN00101315 CN 00101315 CN 00101315 A CN00101315 A CN 00101315A CN 1258690 A CN1258690 A CN 1258690A
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Abstract
Polyamide acid salt solution is first obtained through dissolving aromatic diamine with mixed tetrahydrofuran/methanol solvent in a reactor and the reaction with added aromatic acid anhydride and tertiary amine; and organic clay solution is then formed through adding organic clay into mixed tetrahydrofuran/methanol solvent. The two kinds of solutions are mixed and the mixed solution is poured onto glass plate to be scraped with film forming device into film with required thickness, which is further treated through room temperature and taking down from the glass plate to obtain the film with very low thermal expansion coefficient and containing no residual solvent.
Description
The present invention relates to use inorganics or non-polymer organic material to prepare the method for composite membrane as batching.
Polyimide (PI) is a class high performance polymer material, have outstanding thermotolerance, favorable mechanical performance, dielectric properties, chemical-resistant resistance, radioresistance etc. by its PI film that makes, be widely used in the field that many fields, especially electronics, the space flight and aviation etc. of national economy are rich in the hi-tech composition.Along with the development that science and technology is maked rapid progress, super large-scale integration be applied as electronic product realize light, thin, short, providing for a short time may.Must satisfy material conditions but making to come true, that is exactly that the material of forming electronic product must have the performance of bearing corresponding harsh working conditions.The PI film is formed unicircuit jointly as insulation, protective layer, anti-alpha particle layer and inorganic, metallic substance.Unicircuit can produce big calorimetric in the electronic signal process process, because the thermal expansivity (CTE) of PI is far above inorganic, metallic substance, so phenomenons such as warpage, distortion, be full of cracks take place because of not matching of hot hot expansibility entire circuit, thereby have a strong impact on the reliability of product quality.Therefore the PI film of the low CTE value of development is one of important front edge problem of current material subject.
By compound with inorganic particulate such as clay, preparation PI/ clay nano composite membrane is the effective ways that obtain low CTE value PI film.The existing method that prepare PI/ clay nano composite membrane is to be the PI presoma with polyamic acid (PAA), and organic solvent that employing high boiling point, high polarity, high toxicity and price are higher such as dimethyl formamide (DMF), N,N-DIMETHYLACETAMIDE (DMAc), N-Methyl pyrrolidone (NMP), dimethyl sulfoxide (DMSO) (DMSO) etc. are solvent.Because PAA and above-mentioned solvent have intensive to interact, and form mixture (complex), these solvents can't be got rid of fully in the process of PAA thermal cyclization formation PI; Solvent is pulled out partial polymer in volatilization process from clay layer simultaneously.Therefore the PI/ clay composite membrane that makes of method not only contains residual solvent thus, and the bad dispersibility of clay in polymkeric substance, be difficult to form nanostructure, the stability of composite membrane is not good enough, CTE value (about 40ppm/ ℃) is though purer PI film (about 50～60ppm/ ℃) is low, but still can not satisfy the requirement of electronic industry of future generation, demand further reduction urgently.
The objective of the invention is: with the mixed solvent of methyl alcohol (MeOH) and tetrahydrofuran (THF) (THF) composition, the dissolving aromatic diamines is the preparation method that polyimide (PI) presoma prepares the polyimide/clay nano composite membrane of the ultra low heat expansion coefficient of high comprehensive performance with polyamic acid salt (PAAS).
In order to achieve the above object, the technical solution used in the present invention is that it comprises the steps:
1) in a reaction flask that agitator and thermometer be housed, adds the 0.1mol aromatic diamines down in 20～25 ℃, 380～460g tetrahydrofuran (THF)/methanol mixed solvent, the weight ratio of tetrahydrofuran (THF)/methyl alcohol is 9: 1～4: 6 (being preferably 7: 3), after treating that aromatic diamines dissolves fully, slowly add the equivalent aromatic anhydride, the equivalence ratio of acid anhydrides/aromatic diamines is 1: 0.9～1: 1.1 (being preferably 1: 1.05), after 2～8 hours (best 4 hours) are carried out in reaction, the tertiary amine that adds 1.95～2.5 times of aromatic diamines equivalents, continue 2～8 hours (best 3 hours) of reaction again, promptly obtain xanchromatic polyamic acid salts solution;
2) with organized clay (promptly use clay alteration agent modification after clay), the weight ratio of polyimide/clay is 99: 1～90: 10 (being preferably 97: 3), pour in the mixed solvent of 45～55g tetrahydrofuran (THF)/methyl alcohol composition, the weight ratio of tetrahydrofuran (THF)/methyl alcohol is 9: 1～4: 6 (being preferably 7: 3), stir 1～8 hour (best 3 hours) under the room temperature, form the clayish solution that organises;
3) organized clay solution is poured into by the 1st) in the polyamic acid salts solution that obtains of step, stir 1～8 hour (best 4 hours) under the room temperature after, form polyamic acid salt/organized clay solution;
4) polyamic acid salt/organized clay solution is poured on the clean sheet glass; spread to the film of desired thickness with the speed of 20～40mm/s with film forming device; temperature program(me) oven dry and curing to set under nitrogen protection; 40 ℃/30min+80 ℃/2h+150 ℃/1h+200 ℃/1h+300 ℃/3h or 25 ℃/48h+150 ℃/1h+300 ℃/3h or 40 ℃/30min+300 ℃/3h; temperature rise rate be 1～10 ℃/min (be preferably 5 ℃/min); after curing is finished; naturally cool to room temperature; lightly transparent film is taken off from sheet glass with clean scraper, promptly obtain polyimide/clay nano composite membrane.
Starting material:
1) acid anhydrides: aromatic anhydride, as pyromellitic acid acid anhydride (PDMA), dibenzoic acid dibasic ketonic acid acid anhydride (BPTA) etc.
2) diamines: aromatic diamines, as two amido p-phenylenes (DADE), Ursol D (ODA) etc.
3) tertiary amine: contain the saturated alkyl amine of 1-20 carbon atom and contain the unsaturated alkyl amine of 5-20 carbon atom.As: Trimethylamine, triethylamine, N-dimethyl butylamine, N, N '-dimethylhexylamine, N, N '-dimethyl octylame, N, N '-dioctyl phthalate decyl amine, N, N '-dimethyllaurylamine, N, N '-dimethyl lauryl amine, N, N '-dimethyl hexadecylamine, N, N '-2-butyl-2-DEHA, dimethyl-3-methoxybutyl amine, trivinyl amine, N, N '-dimethyl vinyl amine, N-methyl trivinyl amine, N, N, N ', N '-tetrem thiazolinyl two amido butane etc.
4) clay: polynite (MMT), mica (MICA), lithium montmorillonite etc.
5) clay alteration agent: all can all can use with the promoting agent of clay generation ion exchange, as quarternary ammonium salt, and aluminum alkyls, n-alkyl amino acid or the like.
The present invention compares with background technology, and the useful effect that has is: the PI/ clay nano composite membrane that is made by the present invention does not contain residual solvent, and clay is dispersed excellent and formation nanostructure in polymkeric substance.Composite membrane has excellent comprehensive performances, particularly the ultra low heat expansion coefficient.Under same thickness, the thermal expansivity of the composite membrane that makes has only 10～50% of the composite membrane that makes with existing method.
Be embodiments of the invention below:
Embodiment 1
(1) in a reaction flask that agitator and thermometer be housed, adds 0.1mol aromatic diamines, 380g THF/MeOH mixed solvent (weight ratio of THF/MeOH is 9/1) down in 20～25 ℃.After treating that aromatic diamines dissolves fully, slowly add equivalent aromatic anhydride (equivalence ratio of acid anhydrides/aromatic diamines is 1: 0.9).Reaction carries out adding after 2 hours the triethylamine of 2.0 times of aromatic diamines equivalents, continues reaction 2 hours again, promptly obtains xanchromatic PAAS solution.
(2) (properties-correcting agent is N with organic montmorillonoid, the quarternary ammonium salt that N '-dimethyllaurylamine is become with hydrochloric acid, the weight ratio of PI and organic montmorillonoid is 97: 3) pour in the mixed solvent of 45g THF/MeOH (weight ratio of THF/MeOH is 7/3) composition, stirred 2 hours under the room temperature, form organic montmorillonoid solution.
(3) organic montmorillonoid solution is poured in the PAAS solution that is obtained by (1) step, stirred under the room temperature and form PAAS/ organic montmorillonoid solution after 2 hours.
(4) PAAS/ organic montmorillonoid solution is poured on the clean sheet glass, spreads to the film of desired thickness 280 μ m with film forming device with the speed of 30mm/s.Under nitrogen protection with the temperature program(me) oven dry set with solidify: 25 ℃/48h+150 ℃/1h+300 ℃/3h (temperature rise rate be 5 ℃/min).After finishing, curing naturally cools to room temperature.Lightly transparent film is taken off from sheet glass with clean scraper, promptly obtain PI/ clay nano composite membrane.Its CTE value sees Table 1.
Embodiment 2
(1) in a reaction flask that agitator and thermometer be housed, adds 0.1mol aromatic diamines, 420g THF/MeOH mixed solvent (weight ratio of THF/MeOH is 7/3) down in 20～25 ℃.After treating that aromatic diamines dissolves fully, slowly add equivalent aromatic anhydride (equivalence ratio of acid anhydrides/aromatic diamines 1: 1.05).Reaction carries out adding after 4 hours the triethylamine of 2.25 times of aromatic diamines equivalents, continues reaction 3 hours again, promptly obtains xanchromatic PAAS solution.
(2) (properties-correcting agent is N with organic montmorillonoid, the quarternary ammonium salt that N '-dimethyllaurylamine is become with hydrochloric acid, the weight ratio of PI and organic montmorillonoid is 97: 3) pour in the mixed solvent of 50g THF/MeOH (weight ratio of THF/MeOH is 7/3) composition, stirred 3 hours under the room temperature, form organic montmorillonoid solution.
(3) organic montmorillonoid solution is poured in the PAAS solution that is obtained by (1) step, stirred under the room temperature and form PAAS/ organic montmorillonoid solution after 4 hours.
(4) PAAS/ organic montmorillonoid solution is poured on the clean sheet glass, spreads to the film of desired thickness 350 μ m with film forming device with the speed of 35mm/s.Under nitrogen protection with the temperature program(me) oven dry set with solidify: 40 ℃/30min+80 ℃/2h+150 ℃/1h+200 ℃/1h+300 ℃/3h (temperature rise rate be 5 ℃/min).After finishing, curing naturally cools to room temperature.Lightly transparent film is taken off from sheet glass with clean scraper, promptly obtain PI/ clay nano composite membrane.Its CTE value sees Table 1.
Embodiment 3
(1) in a reaction flask that agitator and thermometer be housed, adds 0.1mol aromatic diamines, 460g THF/MeOH mixed solvent (weight ratio of THF/MeOH is 4/6) down in 20～25 ℃.After treating that aromatic diamines dissolves fully, slowly add equivalent aromatic anhydride (equivalence ratio of acid anhydrides/aromatic diamines is 1: 1.1).Reaction carries out adding after 8 hours the triethylamine of 2.5 times of aromatic diamines equivalents, continues reaction 8 hours again, promptly obtains xanchromatic PAAS solution.
(2) (properties-correcting agent is N with organic montmorillonoid, the quarternary ammonium salt that N '-dimethyllaurylamine is become with hydrochloric acid, the weight ratio of PI and polynite is 90: 10) pour in the mixed solvent of 55g THF/MeOH (weight ratio of THF/MeOH is 4/6) composition, stirred 8 hours under the room temperature, form organic montmorillonoid solution.
(3) organic montmorillonoid solution is poured in the PAAS solution that is obtained by (1) step, stirred under the room temperature and form PAAS/ organic montmorillonoid solution after 8 hours.
(4) PAAS/ organic montmorillonoid solution is poured on the clean sheet glass, spreads to the film of desired thickness 450 μ m with film forming device with the speed of 40mm/s.Under nitrogen protection with the temperature program(me) oven dry set with solidify: 40 ℃/30min+300 ℃/3h.After finishing, curing naturally cools to room temperature.Lightly transparent film is taken off from sheet glass with clean scraper, promptly obtain PI/ clay nano composite membrane.Its CTE value sees Table 1.
Embodiment 4
(1) in a reaction flask that agitator and thermometer be housed, adds 0.1mol aromatic diamines, 420g THF/MeOH mixed solvent (weight ratio of THF/MeOH is 7/3) down in 20～25 ℃.After treating that aromatic diamines dissolves fully, slowly add equivalent aromatic anhydride (equivalence ratio of acid anhydrides/aromatic diamines 1: 1.05).Reaction carries out adding after 4 hours the triethylamine of 2.25 times of aromatic diamines equivalents, continues reaction 3 hours again, promptly obtains xanchromatic PAAS solution.
(2) will organise that (properties-correcting agent is N to mica, the quarternary ammonium salt that N '-dimethyllaurylamine is become with hydrochloric acid, PI is 97: 3 with the micaceous weight ratio that organises) pour in the mixed solvent of 50g THF/MeOH (weight ratio of THF/MeOH is 7/3) composition, stirred 3 hours under the room temperature, form the mica solution that organises.
(3) the mica solution that will organise is poured in the PAAS solution that is obtained by (1) step, stirs under the room temperature and forms the PAAS/ mica solution that organises after 4 hours.
(4) PAAS/ organized clay solution is poured on the clean sheet glass, spreads to the film of desired thickness 350 μ m with film forming device with the speed of 35mm/s.Under nitrogen protection with the temperature program(me) oven dry set with solidify: 40 ℃/30min+80 ℃/2h+150 ℃/1h+200 ℃/1h+300 ℃/3h (temperature rise rate be 5 ℃/min).After finishing, curing naturally cools to room temperature.Lightly transparent film is taken off from sheet glass with clean scraper, promptly obtain PI/ clay nano composite membrane.Its CTE value sees Table 1.
Embodiment 5
(1) in a reaction flask that agitator and thermometer be housed, adds 0.1mol aromatic diamines, 420g THF/MeOH mixed solvent (weight ratio of THF/MeOH is 7/3) down in 20～25 ℃.After treating that aromatic diamines dissolves fully, slowly add equivalent aromatic anhydride (equivalence ratio of acid anhydrides/aromatic diamines 1: 1.05).Reaction carries out adding after 4 hours the N of 2.25 times of aromatic diamines equivalents, and N '-dimethyl octylame continues reaction 3 hours again, promptly obtains xanchromatic PAAS solution.
(2) (properties-correcting agent is the 12-alkyl amino acid with organic montmorillonoid, the weight ratio of PI and organic montmorillonoid is 97: 3) pour in the mixed solvent of 50g THF/MeOH (weight ratio of THF/MeOH is 7/3) composition, stirred 3 hours under the room temperature, form organic montmorillonoid solution.
(3) organic montmorillonoid solution is poured in the PAAS solution that is obtained by (1) step, stirred under the room temperature and form PAAS/ organic montmorillonoid solution after 4 hours.
(4) PAAS/ organic montmorillonoid solution is poured on the clean sheet glass, spreads to the film of desired thickness 350 μ m with film forming device with the speed of 35mm/s.Under nitrogen protection with the temperature program(me) oven dry set with solidify: 40 ℃/30min+80 ℃/2h+150 ℃/1h+200 ℃/1h+300 ℃/3h (temperature rise rate be 5 ℃/min).After finishing, curing naturally cools to room temperature.Lightly transparent film is taken off from sheet glass with clean scraper, promptly obtain PI/ clay nano composite membrane.Its CTE value sees Table 1.
Embodiment 6
(1) in a reaction flask that agitator and thermometer be housed, adds 0.1mol aromatic diamines, 420g THF/MeOH mixed solvent (weight ratio of THF/MeOH is 7/3) down in 20～25 ℃.After treating that aromatic diamines dissolves fully, slowly add equivalent aromatic anhydride (equivalence ratio of acid anhydrides/aromatic diamines 1: 1.05).Reaction carries out adding after 4 hours the N of 2.25 times of aromatic diamines equivalents, and N '-dimethyl octylame continues reaction 3 hours again, promptly obtains xanchromatic PAAS solution.
(2) will organise that (properties-correcting agent is the 12-alkyl amino acid to mica, PI is 97: 3 with the micaceous weight ratio that organises) pour in the mixed solvent of 50g THF/MeOH (weight ratio of THF/MeOH is 7/3) composition, stirred 3 hours under the room temperature, form the mica solution that organises.
(3) the mica solution that will organise is poured in the PAAS solution that is obtained by (1) step, stirs under the room temperature and forms the PAAS/ mica solution that organises after 4 hours.
(4) PAAS/ organized clay solution is poured on the clean sheet glass, spreads to the film of desired thickness 350 μ m with film forming device with the speed of 35mm/s.Under nitrogen protection with the temperature program(me) oven dry set with solidify: 40 ℃/30min+80 ℃/2h+150 ℃/1h+200 ℃/1h+300 ℃/3h (temperature rise rate be 5 ℃/min).After finishing, curing naturally cools to room temperature.Lightly transparent film is taken off from sheet glass with clean scraper, promptly obtain PI/ clay nano composite membrane.Its CTE value sees Table 1.
Embodiment 7
(1) in a reaction flask that agitator and thermometer be housed, adds 0.1mol aromatic diamines, 420g THF/MeOH mixed solvent (weight ratio of THF/MeOH is 7/3) down in 20～25 ℃.After treating that aromatic diamines dissolves fully, slowly add equivalent aromatic anhydride (equivalence ratio of acid anhydrides/aromatic diamines 1: 1.05).Reaction carries out adding after 4 hours the N of 2.25 times of aromatic diamines equivalents, and N '-dimethyl hexadecylamine continues reaction 3 hours again, promptly obtains xanchromatic PAAS solution.
(2) (properties-correcting agent is the 12-alkyl amino acid with organic montmorillonoid, the weight ratio of PI and organic montmorillonoid is 97: 3) pour in the mixed solvent of 50g THF/MeOH (weight ratio of THF/MeOH is 7/3) composition, stirred 3 hours under the room temperature, form organic montmorillonoid solution.
(3) organic montmorillonoid solution is poured in the PAAS solution that is obtained by (1) step, stirred under the room temperature and form PAAS/ organic montmorillonoid solution after 4 hours.
(4) PAAS/ organic montmorillonoid solution is poured on the clean sheet glass, spreads to the film of desired thickness 350 μ m with film forming device with the speed of 35mm/s.Under nitrogen protection with the temperature program(me) oven dry set with solidify: 40 ℃/30min+80 ℃/2h+150 ℃/1h+200 ℃/1h+300 ℃/3h (temperature rise rate be 5 ℃/min).After finishing, curing naturally cools to room temperature.Lightly transparent film is taken off from sheet glass with clean scraper, promptly obtain PI/ clay nano composite membrane.Its CTE value sees Table 1.
The CTE value of table 1 film
| Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Example 6 | Example 7 | |
| Thickness (μ m) | ?21 | ?20 | ?21 | ?22 | ?21 | ?20 | ?22 |
| CTE(ppm/℃) | ?27 | ?23 | ?28 | ?8 | ?20 | ?5 | ?21 |
Claims (3)
1. the preparation method of the polyimide of ultra low heat expansion coefficient/clay nano composite membrane is characterized in that it comprises the steps:
1) in a reaction flask that agitator and thermometer be housed, adds the 0.1mol aromatic diamines down in 20～25 ℃, 380～460g tetrahydrofuran (THF)/methanol mixed solvent, the weight ratio of tetrahydrofuran (THF)/methyl alcohol is 9: 1～4: 6, after treating that aromatic diamines dissolves fully, slowly add the equivalent aromatic anhydride, the equivalence ratio of acid anhydrides/aromatic diamines is 1: 0.9～1: 1.1, after reaction is carried out 2～8 hours, the tertiary amine that adds 1.95～2.5 times of aromatic diamines equivalents, continue reaction 2～8 hours again, promptly obtain xanchromatic polyamic acid salts solution;
2) with organized clay, the weight ratio of polyimide/clay is 99: 1～90: 10, pours in the mixed solvent of 45～55g tetrahydrofuran (THF)/methyl alcohol composition, and the weight ratio of tetrahydrofuran (THF)/methyl alcohol is 9: 1～4: 6, stirred under the room temperature 1～8 hour, and formed the clayish solution that organises;
3) organized clay solution is poured into by the 1st) in the polyamic acid salts solution that obtains of step, stir 1～8 hour under the room temperature after, form polyamic acid salt/organized clay solution;
4) polyamic acid salt/organized clay solution is poured on the clean sheet glass; spread to the film of desired thickness with the speed of 20～40mm/s with film forming device; temperature program(me) oven dry and curing to set under nitrogen protection; 40 ℃/30min+80 ℃/2h+150 ℃/1h+200 ℃/1h+300 ℃/3h or 25 ℃/48h+150 ℃/1h+300 ℃/3h or 40 ℃/30min+300 ℃/3h; temperature rise rate is 1～10 ℃/min; after curing is finished; naturally cool to room temperature; lightly transparent film is taken off from sheet glass with clean scraper, promptly obtain polyimide/clay nano composite membrane.
2. the preparation method of the polyimide of ultra low heat expansion coefficient according to claim 1/clay nano composite membrane is characterized in that it comprises the steps:
1) in a reaction flask that agitator and thermometer be housed, adds the 0.1mol aromatic diamines down in 20～25 ℃, 380～460g tetrahydrofuran (THF)/methanol mixed solvent, the weight ratio of tetrahydrofuran (THF)/methyl alcohol is 7: 3, after treating that aromatic diamines dissolves fully, add the equivalent aromatic anhydride, the equivalence ratio of acid anhydrides/aromatic diamines is 1: 1.05, after reaction is carried out 4 hours, the tertiary amine that adds 1.95～2.5 times of aromatic diamines equivalents continues reaction 3 hours again, promptly obtains xanchromatic polyamic acid salts solution;
2) with organized clay, the weight ratio of polyimide/clay is 97: 3, pours in the mixed solvent of 45～55g tetrahydrofuran (THF)/methyl alcohol composition, and the weight ratio of tetrahydrofuran (THF)/methyl alcohol is 7: 3, stirs 3 hours under the room temperature, forms the clayish solution that organises;
3) organized clay solution is poured into by the 1st) in the polyamic acid salts solution that obtains of step, stir under the room temperature after 4 hours, form polyamic acid salt/organized clay solution;
4) polyamic acid salt/organized clay solution is poured on the clean sheet glass; spread to the film of desired thickness with the speed of 20～40mm/s with film forming device; temperature program(me) oven dry and curing to set under nitrogen protection; 40 ℃/30min+80 ℃/2h+150 ℃/1h+200 ℃/1h+300 ℃/3h or 25 ℃/48h+150 ℃/1h+300 ℃/3h or 40 ℃/30min+300 ℃/3h; temperature rise rate is 5 ℃/min; after curing is finished; naturally cool to room temperature; lightly transparent film is taken off from sheet glass with clean scraper, promptly obtain polyimide/clay nano composite membrane.
3. the preparation method of the polyimide of ultra low heat expansion coefficient according to claim 1 and 2/clay nano composite membrane is characterized in that:
1) acid anhydrides: aromatic anhydride, as pyromellitic acid acid anhydride (PDMA), dibenzoic acid dibasic ketonic acid acid anhydride (BPTA);
2) diamines: aromatic diamines, as two amido p-phenylenes (DADE), Ursol D (ODA);
3) tertiary amine: contain the saturated alkyl amine of 1-20 carbon atom and contain the unsaturated alkyl amine of 5-20 carbon atom.As: Trimethylamine, triethylamine, N-dimethyl butylamine, N, N '-dimethylhexylamine, N, N '-dimethyl octylame, N, N '-dioctyl phthalate decyl amine, N, N '-dimethyllaurylamine, N, N '-dimethyl lauryl amine, N, N '-dimethyl hexadecylamine, N, N '-2-butyl-2-7 base hexyl amine, dimethyl-3-methoxybutyl amine, trivinyl amine, N, N '-dimethyl vinyl amine, N-methyl trivinyl amine, N, N, N ', N '-tetrem thiazolinyl two amido butane;
4) clay: polynite (MMT), mica (MICA), lithium montmorillonite;
5) clay alteration agent: all can all can use with the promoting agent of clay generation ion exchange, as quarternary ammonium salt, and aluminum alkyls, n-alkyl amino acid.
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| WO2003066740A1 (en) | 2002-02-06 | 2003-08-14 | Sekisui Chemical Co., Ltd. | Resin composition |
| CN1300251C (en) * | 2004-03-25 | 2007-02-14 | 中国科学院化学研究所 | Polyimide film and its prepn process and use |
| CN100350003C (en) * | 2005-01-21 | 2007-11-21 | 桂林工学院 | Polyimide/inorganic nano-composite insulating varnish and its preparation method |
| CN100402134C (en) * | 2005-04-26 | 2008-07-16 | 哈尔滨工业大学 | Method for preparing polymer/montmorillnoite nano composite hydrophilic membrance |
| CN101374766B (en) * | 2006-01-31 | 2012-07-18 | 独立行政法人产业技术综合研究所 | Clay film and method for producing same |
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| CN1055706C (en) * | 1996-06-05 | 2000-08-23 | 中国科学院化学研究所 | Polyamide and clay nm composite and its prepn. |
| CN1081207C (en) * | 1997-07-17 | 2002-03-20 | 中国科学院化学研究所 | Nanometer composite polyamide-clay material and its preparation |
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| CN100350003C (en) * | 2005-01-21 | 2007-11-21 | 桂林工学院 | Polyimide/inorganic nano-composite insulating varnish and its preparation method |
| CN100402134C (en) * | 2005-04-26 | 2008-07-16 | 哈尔滨工业大学 | Method for preparing polymer/montmorillnoite nano composite hydrophilic membrance |
| CN101374766B (en) * | 2006-01-31 | 2012-07-18 | 独立行政法人产业技术综合研究所 | Clay film and method for producing same |
| CN103360763A (en) * | 2006-06-26 | 2013-10-23 | 沙伯基础创新塑料知识产权有限公司 | Articles comprising a polyimide solvent cast film having a low coefficient of thermal expansion and a method of manufacture thereof |
| CN101627074B (en) * | 2006-06-26 | 2014-02-12 | 沙伯基础创新塑料知识产权有限公司 | Articles comprising polyimide solvent cast film having low coefficient of thermal expansion and method of manufacture thereof |
| CN103694702A (en) * | 2006-06-26 | 2014-04-02 | 沙伯基础创新塑料知识产权有限公司 | Polyimide solvent cast films having a low coefficient of thermal expansion and method of manufacture thereof |
| CN105111476A (en) * | 2015-09-16 | 2015-12-02 | 安徽鑫柏格电子股份有限公司 | Preparation method for polyimide film |
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